A long-standing aim in molecular self-assembly is the development of synthetic nanopores capable of mimicking the mass-transport characteristics of biological channels and pores. Here we report a strategy for enforcing the nanotubular assembly of rigid macrocycles in both the solid state and solution based on the interplay of multiple hydrogen-bonding and aromatic π − π stacking interactions. The resultant nanotubes have modifiable surfaces and inner pores of a uniform diameter defined by the constituent macrocycles. The self-assembling hydrophobic nanopores can mediate not only highly selective transmembrane ion transport, unprecedented for a synthetic nanopore, but also highly efficient transmembrane water permeability. These results establish a solid foundation for developing synthetically accessible, robust nanostructured systems with broad applications such as reconstituted mimicry of defined functions solely achieved by biological nanostructures, molecular sensing, and the fabrication of porous materials required for water purification and molecular separations.

Important interfacial processes in disciplines ranging from medicine to the separations sciences occur over a wide range of pressures, temperatures, and time scales. In this paper we report a new high-pressure total internal reflection fluorescence (HP-TIRF) apparatus that allows rapid fluorescence measurements of sub-monolayers in contact with liquids and supercritical fluids between 293 K and 353 K and up to 250 bar with picosecond time resolution. We use the HP-TIRF system to study the in-plane rotational reorientation dynamics of the fluorescent probe BODIPY 494/503 (C(2v) symmetry) covalently attached to silica surfaces that have been silanized with n-propyltrimethoxysilane (C(3)-TMOS) or 3,3,3-trifluoropropyltrimethoxysilane (CF(3)-TMOS) when the interface is subjected to pure supercritical carbon dioxide (scCO(2)). The in-plane BODIPY 494/503 rotational reorientation dynamics are assessed by using the Debye-Stokes-Einstein expression. As the scCO(2) density increases the local microviscosity surrounding the tethered BODIPY 494/503 molecule decreases. The terminal group (CH(3) versus CF(3)) within the silane monolayer governs the onset and absolute magnitude of the observed viscosity changes. The results are explained in terms of the wellknown solubility of fluorine-containing species in scCO(2).

We report on the rotational reorientation dynamics of a fluorescent reporter molecule, BODIPY 494/503, within n-alkyl (n = 1−18) monolayers formed on quartz in contact with pure supercritical carbon dioxide (scCO 2 ) at 313 K (reduced temperature, T r = 1.03) between a reduced CO 2 density (ρ r = ρ exp /ρ c ) of 0 and 1.8. The BODIPY 494/504 rotational dynamics are described by free (n ≥ 4) and hindered rotor (n ≤ 6) models. As the CO 2 density increases, hindered rotation shifts toward free rotation, and the local viscosity in the cybotactic region surrounding the BODIPY 494/504 reporter within the monolayer decreases. These results are interpreted in terms of n-and density-dependent scCO 2 alkyl chain solvation.